On peroxymonosulfate-based treatment of saline wastewater: when phosphate and chloride co-exist

Sheng, Bo; Huang, Ying; Wang, Zhaohui; Liu, Jianshe

doi:10.1039/c8ra00600h

Cited by 29 publications

(9 citation statements)

References 48 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This has caused some erroneous claims of the positive effects of Cl – on persulfate-AOP, , since HOCl, which has a much longer lifetime, can become the main oxidant in high Cl – conditions, contrary to the intention of utilizing SO 4 •– . Two-electron oxidation of halide ions by PMS ( k (Cl – ) = 2.1 × 10 –3 M –1 s –1 , k (Br – ) = 7.0 × 10 –1 M –1 s –1 , and k (I – ) = 1.4 × 10 3 M –1 s –1 ) leads to direct HOX formation involving no halide-containing radicals as intermediates (Figures b and c), which creates binary mixtures of PMS and halide (e.g., PMS/Cl – , PMS/Br – , PMS/I – ) that can oxidize selected electron-rich organics. ,− Note that mixtures of PMS and salts of Cl – and Br – are used for the synthesis of chlorinated and brominated olefins …”

Section: Sulfate Radical and Persulfate: Matrix Effectsmentioning

confidence: 99%

Persulfate-Based Advanced Oxidation: Critical Assessment of Opportunities and Roadblocks

Lee

Gunten

Kim

2020

Environ. Sci. Technol.

2,151

936

View full text Add to dashboard Cite

Reports that promote persulfate-based advanced oxidation process (AOP) as a viable alternative to hydrogen peroxide-based processes have been rapidly accumulating in recent water treatment literature. Various strategies to activate peroxide bonds in persulfate precursors have been proposed and the capacity to degrade a wide range of organic pollutants has been demonstrated. Compared to traditional AOPs in which hydroxyl radical serves as the main oxidant, persulfate-based AOPs have been claimed to involve different in situ generated oxidants such as sulfate radical and singlet oxygen as well as nonradical oxidation pathways. However, there exist controversial observations and interpretations around some of these claims, challenging robust scientific progress of this technology toward practical use. This Critical Review comparatively examines the activation mechanisms of peroxymonosulfate and peroxydisulfate and the formation pathways of oxidizing species. Properties of the main oxidizing species are scrutinized and the role of singlet oxygen is debated. In addition, the impacts of water parameters and constituents such as pH, background organic matter, halide, phosphate, and carbonate on persulfate-driven chemistry are discussed. The opportunity for niche applications is also presented, emphasizing the need for parallel efforts to remove currently prevalent knowledge roadblocks.

show abstract

Section: Sulfate Radical and Persulfate: Matrix Effectsmentioning

confidence: 99%

Persulfate-Based Advanced Oxidation: Critical Assessment of Opportunities and Roadblocks

Lee

Gunten

Kim

2020

Environ. Sci. Technol.

2,151

936

View full text Add to dashboard Cite

show abstract

“…Like other green oxidants such as O 2 and H 2 O 2 [ 5 ], peroxymonosulfate (PMS, Oxone ® ) has been widely used: (1) in the academia to develop new synthetic protocols [ 6 ]; (2) in pharmaceutical companies to promote oxidative stress testing of active pharmaceutical ingredients (API) to predict their degradation [ 7 ]; and (3) in hypersaline industrial wastewaters to remove organic contaminants [ 8 , 9 , 10 ]. This safe, sustainable, and inexpensive oxidant has shown extraordinary reactivity with alkaline metal halide salts [ 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 , 26 , 27 ] and with hydrogen halides (HCl, HBr and HI) [ 28 , 29 , 30 ].…”

Section: Introductionmentioning

confidence: 99%

Selective Oxidation of Clopidogrel by Peroxymonosulfate (PMS) and Sodium Halide (NaX) System: An NMR Study

Krake

Baumann

2021

Molecules

View full text Add to dashboard Cite

A selective transformation of clopidogrel hydrogen sulfate (CLP) by reactive halogen species (HOX) generated from peroxymonosulfate (PMS) and sodium halide (NaX) is described. Other sustainable oxidants as well as different solvents have also been investigated. As result of this study, for each sodium salt the reaction conditions were optimized, and four different degradation products were formed. Three products were halogenated at C-2 on the thiophene ring and have concomitant functional transformation, such as N-oxide in the piperidine group. A halogenated endo-iminium product was also observed. With this condition, a fast preparation of known endo-iminium clopidogrel impurity (new counterion) was reported as well. The progress of the reaction was monitored using nuclear magnetic resonance spectroscopy as an analytical tool and all the products were characterized by 1D-, 2D-NMR and HRMS.

show abstract

“…The observation that ∼95% of PH was decomposed within 60 min in the binary mixture of PMS and Cl − at 25 °C (Figure S1) implies the occurrence of HOCl as a secondary oxidant via the nucleophilic addition of Cl − to PMS, as previously reported elsewhere. 1,18 Since the activation energy (E a ) of PH chlorination by HOCl is 58.5 kJ mol −1 , 26 heating the binary PMS-Cl − mixture to a temperature of 60 °C would improve the PH treatment efficiency by only ca. 13 times, assuming that the transferred heat was involved predominantly in increasing the rate of the endothermic reaction between PH and HOCl.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…In nucleophilic addition reactions, PMS transfers oxygen atoms to specific anions (i.e., HSO 5 – + A → HSO 4 – + AO , ) as a two-electron oxidant, potentially yielding secondary oxidants such as HOX/OX – ,, and HCO 4 – . Anion-derived nonradical oxidants are capable of selective oxidation of electron-rich organics even without adding activators , or further improving the treatment performance of PMS activation processes . The enhancing effects of select inorganic anions are unique to PMS, whereas the anionic nucleophiles are almost inert to PDS as a symmetrical peroxide.…”

Section: Introductionmentioning

confidence: 99%

Chloride-Mediated Enhancement in Heat-Induced Activation of Peroxymonosulfate: New Reaction Pathways for Oxidizing Radical Production

Ahn

Choi

Kim

et al. 2021

Environ. Sci. Technol.

112

View full text Add to dashboard Cite

This study is the first to demonstrate the capability of Cl − to markedly accelerate organic oxidation using thermally activated peroxymonosulfate (PMS) under acidic conditions. The treatment efficiency gain allowed heat-activated PMS to surpass heat-activated peroxydisulfate (PDS). During thermal PMS activation at excess Cl − , accelerated oxidation of 4-chlorophenol (susceptible to oxidation by hypochlorous acid (HOCl)) was observed along with significant degradation of benzoic acid and ClO 3 − occurrence, which involved oxidants with low substrate specificity. This indicated that heat facilitated HOCl formation via nucleophilic Cl − addition to PMS and enabled free chlorine conversion into less selective oxidizing radicals. HOCl acted as a key intermediate in the major oxidant transition based on temperaturedependent variation in HOCl concentration profiles, kinetically retarded organic oxidation upon NH 4 + addition, and enabled rapid organic oxidation in heated PMS/HOCl mixtures. Chlorine atom that formed via the one-electron oxidation of Cl − by the sulfate radical served as the primary oxidant and was involved in hydroxyl radical production. This was corroborated by the quenching effects of alcohols and bicarbonates, reactivity toward multiple organics, and electron paramagnetic resonance spectral features. PMS outperformed PDS in degrading benzoic acid during thermal activation operated in reverse osmosis concentrate, which was in conflict with the wellestablished superiority of heat-activated PDS.

show abstract

On peroxymonosulfate-based treatment of saline wastewater: when phosphate and chloride co-exist

Abstract: Both chloride and phosphate are common inorganic anions in industrial wastewater, however, their effects on peroxymonosulfate (PMS)-based oxidation systems are largely unknown.

Cited by 29 publications

References 48 publications

Persulfate-Based Advanced Oxidation: Critical Assessment of Opportunities and Roadblocks

Persulfate-Based Advanced Oxidation: Critical Assessment of Opportunities and Roadblocks

Selective Oxidation of Clopidogrel by Peroxymonosulfate (PMS) and Sodium Halide (NaX) System: An NMR Study

Chloride-Mediated Enhancement in Heat-Induced Activation of Peroxymonosulfate: New Reaction Pathways for Oxidizing Radical Production

Contact Info

Product

Resources

About